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Asymmetric Epoxidation vs syn-Hydroxy-Acyloxylation of Olefins in the Presence of Sterically Demanding Nonheme Manganese Complexes Научная публикация

Журнал ACS Catalysis
ISSN: 2155-5435
Вых. Данные Год: 2024, Том: 14, Номер: 1, Страницы: 498-507 Страниц : 10 DOI: 10.1021/acscatal.3c04832
Авторы Sherstyuk Varvara A. 1,2 , Ottenbacher Roman V. 1 , Talsi Evgenii P. 1 , Bryliakov Konstantin P. 3
Организации
1 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
2 Novosibirsk State University, Pirogova 1, Novosibirsk 630090, Russia
3 Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr. 47, Moscow 119991, Russia

Реферат: Herewith, we present another facet of the versatile catalytic reactivity of bulky bis-amino-bis-pyridylmethyl Mn complexes: besides highly enantioselective (up to 99% ee) epoxidation, benzhydryl-substituted Mn catalysts have been found to convert olefinic substrates into the products of syn-addition to the C═C bond, hydroxy-carboxylates, that can prevail under certain conditions. The mechanism of syn-hydroxy-acyloxylation is discussed, with the data obtained providing evidence in favor of the so far lacking direct enantioselective OH and OC(O)R transfer from the high-valent Mn active species to the olefinic C═C group. Such a mechanism is conceptually reminiscent of Rieske dioxygenases that catalyze enantioselective 1,2-dihydroxylation of C═C bonds, simultaneously incorporating two cis-ligands from the reactive metal center into the resulting diol in a syn-selective fashion.
Библиографическая ссылка: Sherstyuk V.A. , Ottenbacher R.V. , Talsi E.P. , Bryliakov K.P.
Asymmetric Epoxidation vs syn-Hydroxy-Acyloxylation of Olefins in the Presence of Sterically Demanding Nonheme Manganese Complexes
ACS Catalysis. 2024. V.14. N1. P.498-507. DOI: 10.1021/acscatal.3c04832 WOS Scopus OpenAlex
Идентификаторы БД:
Web of science: WOS:001137558600001
Scopus: 2-s2.0-85181805299
OpenAlex: W4390114514
Цитирование в БД:
БД Цитирований
OpenAlex 11
Scopus 9
Web of science 7
Альметрики: